CN116195108A

CN116195108A - Pmn2 as lithium super ion conductor, solid electrolyte and coating for lithium metal and lithium ion batteries 1 LiZnCl in space group 4 Derivatives and their use as inhibitors of viral infection

Info

Publication number: CN116195108A
Application number: CN202180044591.0A
Authority: CN
Inventors: 莫一非; Y·刘; 凌晨
Original assignee: Toyota Motor Corp; University of Maryland at College Park
Current assignee: Toyota Motor Corp; University of Maryland at College Park
Priority date: 2020-06-23
Filing date: 2021-06-23
Publication date: 2023-05-30
Also published as: US20210399333A1; WO2021260584A1; JP2023531235A

Abstract

The invention provides a compound having Pmn2 ₁ Solid state lithium ion electrolytes of lithium zinc chloride derived compounds in crystalline form in space groups are useful as materials for conducting lithium ions. The activation energy of the lithium aluminum chloride derived compound is 0.15 to 0.40eV and the conductivity is 0.01 to 15mS/cm at 300K. The present invention provides compounds of specific formulas and methods of altering materials by including the indicated aliovalent ions. The invention also provides lithium batteries containing the composite lithium ion electrolyte and electrodes containing lithium aluminum chloride derived compounds.

Description

Pmn2 as lithium super ion conductor, solid electrolyte and coating for lithium metal and lithium ion batteries 1 LiZnCl in space group 4 Derivatives and their use as inhibitors of viral infection

Names of parties to a joint research agreement

The disclosure herein was the result of joint research work conducted in accordance with the joint research agreement between Toyota automobile engineering and manufacturing North American Co., ltd (address: 6565Headquarters Drive W1-3C, plano, texas, 75024) and the university of Maryland, parker, address: 2130Mitchell Bldg.7999Regents Dr.Colledge Park,Maryland,20742.

Technical Field

The present disclosure relates to a plant having Pmn2 ₁ Novel LiZnCl with high lithium ion conductivity of crystal structure of space group ₄ Derivative compounds useful as solid electrolytes and electrode components and/or electrode coatings for lithium ion and lithium metal batteries.

Background

Lithium ion batteries have traditionally dominated the market for portable electronic devices. However, conventional lithium ion batteries contain flammable organic solvents as components of the electrolyte, and this flammability is the basis for safety risks that are of concern and may limit or prevent the use of lithium ion batteries for large-scale energy storage.

Replacement of flammable organic liquid electrolytes with solid Li-conducting phases would alleviate this safety problem and may provide additional advantages such as improved mechanical and thermal stability. The main function of the solid Li-conducting phase (commonly referred to as solid Li-ion conductor or solid electrolyte) is to carry Li during discharge ⁺ Ions are conducted from the anode side to the cathode side and from the cathode side to the anode side during charging while blocking direct transport of electrons between electrodes within the cell.

Further, it is known that lithium batteries constructed with nonaqueous electrolytes form dendritic lithium metal structures protruding from the anode to the cathode during repeated discharge and charge cycles. If and when such dendrite structures protrude to the cathode and short circuit, the battery energy is rapidly released and ignition of the organic solvent may be initiated.

Accordingly, there has been a constant interest and effort in finding new solid Li-ion conducting materials that would lead to all-solid lithium batteries. Research over the past decades has focused mainly on ion-conducting oxides, such as LISICON (Li) ₁₄ ZnGe ₄ O ₁₆ )、NASICON(Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ ) Perovskite (e.g. La _0.5 Li _0.5 TiO ₃ ) Garnet (Li) ₇ La ₃ Zr ₂ O ₁₂ ) LiPON (e.g. Li _2.88 PO _3.73 N _0.14 ) And sulfides such as Li ₃ PS ₄ 、Li ₇ P ₃ S ₁₁ And LGPS (Li) ₁₀ GeP ₂ S ₁₂ )。

While recent developments have scaled the conductivity of solid lithium ion conductors to a level of 1-10mS/cm, which is comparable to that in liquid phase electrolytes, it is of great interest to find new solid lithium ion conductors.

An effective lithium ion solid conductor will have high Li at room temperature ⁺ Conductivity. In general, li ⁺ Conductivity is not less than 10 ^-6 S/cm. In addition, li in conductor ⁺ The activation energy of migration must be low to be useful over the range of operating temperatures that may be encountered in the environment. Furthermore, the material should have good stability against chemical, electrochemical and thermal degradation. Unlike many conventionally used nonaqueous solvents, solid conductor materials should be stable to electrochemical degradation reactivity of the anode and cathode chemistries. The material should have low grain boundary resistance for use in all solid state batteries. Ideally, the synthesis of the material should be easy and should not be costly.

The standard redox potential of Li/Li+ is-3.04V, making lithium metal one of the strongest reducing agents available. Thus, li metal is able to reduce most known cationic species to a lower oxidation state. Due to this strong reducing ability, when the lithium metal of the anode contacts solid Li containing a cation component different from lithium ions ⁺ In the case of conductors, lithium will be cationicThe species reduces to a lower oxidation state and degrades the solid conductor.

Thus, many of the currently conventionally known solid Li-ion conductors suffer from stability problems when in contact with Li metal anodes.

The inventors of the present application have studied lithium compounds that are available for future use of solid li+ conductors, and previous results of the present study are disclosed in U.S. application No. 15/626696, U.S. application No. 16/805672, U.S. application No. 16/013495, U.S. application No. 16/114946, U.S. application No. 16/142217, U.S. application No. 16/144157, U.S. application No. 16/153335, U.S. application No. 16/155349, U.S. application No. 16/264294, U.S. application No. 16/570811, and U.S. application No. 16/57888. However, research efforts continue to find additional materials that have maximum efficiency, high stability, low cost, and ease of handling and manufacture.

It is therefore an object of the present application to identify a range of further materials which have a high Li-ion conductivity and are poor electron conductors, which are suitable as solid electrolytes and/or electrode components for lithium-ion and lithium-metal batteries.

It is another object of the present application to provide solid state lithium ion and/or lithium metal batteries containing these materials with high Li ion conductivity and are poor electron conductors.

Disclosure of Invention

These and other objects are provided by embodiments of the present application, a first embodiment of which includes a solid state lithium ion electrolyte comprising: at least one material selected from the group of materials consisting of compounds of formulae (I), (II), (III) and (IV):

Li _x-y (M1) _y ZnCl ₄ (I)

wherein the method comprises the steps of

y is a number greater than 0 and less than 2, x is a value such that charge neutrality of the formula is obtained, and M1 is at least one element other than Li selected from elements of groups 1, 2, and 13;

Li _x Zn _1-z (M2) _z Cl ₄ (II)

wherein the method comprises the steps of

z is a number greater than 0 and less than 1, x is a value such that formula (II) is charge neutral, and M2 is at least one element other than Zn selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, and 17;

Li _x ZnCl _4-h (X) _h (III)

wherein the method comprises the steps of

h is greater than 0 and less than 4, X is a value such that formula (III) is charge neutral, and X is at least one element other than Cl selected from the elements of groups 16 and 17; and

Li _x-m (M1) _m Zn _1-n (M2) _n Cl _4-o (X) _o (IV)

wherein the method comprises the steps of

m is a number from 0 to less than 2, n is a number from 0 to less than 1, o is a number from 0 to less than 4, and x is a value such that formula (IV) is charge neutral, provided that at least two of m, n and o cannot be 0,

wherein the compounds of formulae (I), (II), (III) and (IV) comprise compounds having the steric group Pmn2 ₁ And is of rhombohedral phase lattice structure

Provided that the content of M1, M2 and/or X is such that the compound is Pmn2 ₁ The value at which the structure is maintained.

In one aspect of the first embodiment, the solid state lithium ion electrolytes of formulas (I) through (IV) are lithium ions (Li) ⁺ ) The conductivity is 0.1 to 15mS/cm at 300K.

In another aspect of the first embodiment, the complexes of formulas (I) through (IV) have an activation energy of 0.15 to 0.40eV.

In a second embodiment, a solid state lithium battery is provided. The battery includes:

an anode;

a cathode; and

a solid lithium ion electrolyte between the anode and the cathode,

wherein the solid lithium ion electrolyte comprises at least one material selected from the group of materials consisting of compounds of formulas (I), (II), (III), and (IV):

Li _x-y (M1) _y ZnCl ₄ (I)

wherein the method comprises the steps of

Li _x Zn _1-z (M2) _z Cl ₄ (II)

wherein the method comprises the steps of

Li _x ZnCl _4-h (X) _h (III)

wherein the method comprises the steps of

Li _x-m (M1) _m Zn _1-n (M2) _n Cl _4-o (X) _o (IV)

wherein the method comprises the steps of

The lithium battery of the second embodiment may be a lithium metal battery or a lithium ion battery.

In a third embodiment, an electrode for a solid state lithium battery is provided. The electrode comprises:

a current collector; and

an electrode active layer on the current collector,

wherein the electrode active layer includes at least one compound selected from the group consisting of compounds of formulas (I), (II), (III), and (IV):

Li _x-y (M1) _y ZnCl ₄ (I)

wherein the method comprises the steps of

Li _x Zn _1-z (M2) _z Cl ₄ (II)

wherein the method comprises the steps of

Li _x ZnCl _4-h (X) _h (III)

wherein the method comprises the steps of

Li _x-m (M1) _m Zn _1-n (M2) _n Cl _4-o (X) _o (IV)

wherein the method comprises the steps of

In a fourth embodiment, an electrode for a solid state lithium battery is provided. The electrode comprises:

a current collector;

an electrode active layer on the current collector; and

a coating layer on the electrode active layer,

wherein the coating on the electrode active layer comprises at least one compound selected from the group consisting of compounds of formulas (I), (II), (III), and (IV):

Li _x-y (M1) _y ZnCl ₄ (I)

wherein the method comprises the steps of

Li _x Zn _1-z (M2) _z Cl ₄ (II)

wherein the method comprises the steps of

Li _x ZnCl _4-h (X) _h (III)

wherein the method comprises the steps of

Li _x-m (M1) _m Al _1-n (M2) _n Cl _4-o (X) _o (IV)

wherein the method comprises the steps of

Solid state lithium batteries containing the electrodes and/or electrolytes of the various embodiments and aspects thereof are also provided. The solid state lithium battery may be a lithium metal battery or a lithium ion battery.

The foregoing description is intended to provide a general description and overview of the present disclosure, and is not intended to limit the present disclosure unless explicitly stated otherwise. The presently preferred embodiments, together with further advantages, will be best understood by reference to the following detailed description taken in conjunction with the accompanying drawings.

Drawings

The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the patent office upon request and payment of the necessary fee.

FIG. 1 shows Pmn2 ₁ Li of space group ₂ ZnCl ₄ Is a crystal structure of (a).

FIG. 2 shows Pmn2 ₁ Li of space group ₂ ZnCl ₄ XRD analysis of the crystal structure of (c).

FIG. 3 shows the list and Li in FIG. 2 ₂ ZnCl ₄ A table of peak positions and intensities of peaks having a maximum intensity compared to peaks having a relative intensity of 1 or more in XRD analysis.

FIG. 4 shows Pmn2 ₁ Li of space group _1.5 Zn _0.5 Al _0.5 Cl ₄ Is a crystal structure of (a).

FIG. 5 shows Pmn2 ₁ Li of space group _1.5 Zn _0.5 Al _0.5 Cl ₄ XRD analysis of the crystal structure of (c).

FIG. 6 shows the list and Li in FIG. 5 _1.5 Zn _0.5 Al _0.5 Cl ₄ A table of peak positions and intensities of peaks having a maximum intensity compared to peaks having a relative intensity of 1 or more in XRD analysis.

FIG. 7 shows Pmn2 ₁ Li of space group _1.25 Al _0.75 Zn _0.25 Cl ₄ Is a crystal structure of (a).

FIG. 8 shows Pmn2 ₁ Li of space group _1.25 Al _0.75 Zn _0.25 Cl ₄ XRD analysis of the crystal structure of (c).

FIG. 9 shows Li from FIG. 8 _1.75 Al _0.75 Zn _0.25 Cl ₄ A table of peak positions and intensities of peaks having a maximum intensity compared to peaks having a relative intensity of 1 or more in XRD analysis.

FIG. 10 shows Li obtained from AIMD simulation ₂ ZnCl ₄ Arrhenius diagram of lithium ion diffusivity D in (a).

FIG. 11 shows Li obtained from AIMD simulation ₂ ZnCl ₄ The probability density of lithium ions in (a).

FIG. 12 shows Li obtained from AIMD simulation _1.5 Zn _0.5 Al _0.5 Cl ₄ The probability density of lithium ions in (a).

FIG. 13 shows Li obtained from AIMD simulation _1.25 Al _0.75 Zn _0.25 Cl ₄ The probability density of lithium ions in (a).

Detailed Description

Throughout the specification, the terms "electrochemical cell" and "battery" may be used interchangeably unless the context of the specification clearly distinguishes an electrochemical cell from a battery. Furthermore, the terms "solid electrolyte" and "solid ionic conductor" may be used interchangeably unless specifically indicated otherwise.

Concerning known Li ⁺ Ion conductor Li ₁₀ GeP ₂ S ₁₂ And Li (lithium) ₇ P ₃ S ₁₁ Ceder et al (Nature Materials,14, 2015, 1026-1031) have described effective Li ⁺ The structural characteristics of the conductive lattice, in which the sulfur sublattice of the two materials is shown to very closely match the bcc lattice structure. In addition, it is shown that Li is coordinated across adjacent tetrahedra ⁺ Li of lattice sites ⁺ Ion hopping provides the path of lowest activation energy.

The present inventors are conducting continuous research on new lithium composite compounds to identify materials having properties useful as solid electrolytes in solid-state lithium batteries. During this ongoing research effort, the inventors have developed and implemented methods for identifying composite materials having chemical and structural properties that have been determined by the inventors to be suitable indicators of lithium ion conduction as a component of the solid state electrolyte and electrodes adjacent to the solid state electrolyte of lithium ion batteries.

In order to qualify as a solid-state electrolyte in practical applications, the material must meet several specific criteria. First, it should exhibit a desired lithium ion conductivity, typically not less than 10 at room temperature ^-6 S/cm. Second, the material should have good stability against chemical, electrochemical and thermal degradation. Third, the material should have low grain boundary resistance for all-solid batteries. Fourth, the synthesis of the material should be easy and not costly.

The standard requirements of the process are that in order to qualify as a solid electrolyte in practical applications, the material must exhibit the desired lithium ion conductivity at room temperature, typically not less than 10 ^-6 S/cm. Thus, de novo computational molecular dynamics modeling studies were applied to calculate the diffusivity of lithium ions in the lattice structure of selected silicate materials. To accelerate the simulation, the calculations were performed at high temperature and the effect of excess Li or Li vacancies was considered. In order to generate excess Li or Li vacancies, the aliovalent substitution of cations or anions can be evaluated. Thus, li vacancies are created by, for example, partially replacing Si with aliovalent cationic species while compensating for charge neutrality with Li vacancies or excess Li. For example, substitution of Li with P ₁₀ Si ₂ PbO ₁₀ 50% of Si in (B) results in the formation of Li ₉ PSiPbO ₁₀ 。

According to equation (I), the diffusivity at 300K is determined,

D＝D ₀ exp(-E _a /k _b t) equation (I)

Wherein D is ₀ 、E _a And k _b Respectively, the pre-factor, activation energy and boltzmann constant. According to equation (II) Conductivity is related to calculated diffusivity:

σ＝D ₃₀₀ ρe ² /k _b t equation (II)

Where ρ is the bulk density of lithium ions and e is the unit charge.

The anionic lattice of Li ion conductors has been shown to match some lattice types (see Nature Materials,14, 2015, 2016). Thus, potential Li ⁺ Anionic lattice of ion conductor and Li known to have high conductivity ⁺ Anionic lattice comparison of ion conductors.

Thus, the selected lithium aluminum chloride derived compounds were compared with Li-containing compounds reported in the inorganic crystal structure database (FIZ Karlsruhe ICSD-https:// ics d. Fiz-karlsruhe. De) and an anionic lattice matching method was evaluated, developed by the inventors in accordance with this objective and described in co-pending U.S. application No. 15/597651 filed on 5/17 of 2017, to match the lattices of these compounds to known lithium ion conductors.

According to the anionic lattice matching method described in co-pending U.S. application No. 15/597651, the atomic coordinate system of the compound lattice structure can be converted to a coordinate system for the anionic lattice only. The anions of the lattice are replaced by anions of the comparative material and the resulting unit cell is rescaled. X-ray diffraction data for the modified anion-only lattice can be simulated and an n x 2 matrix generated from the simulated diffraction data. Quantitative structural similarity values may be derived from an n x 2 matrix.

The purpose of anionic lattice matching is to further identify the potential with maximum to exhibit high Li ⁺ Conductivity compounds. From this work, the compounds described in the following embodiments were determined to be likely suitable as solid Li ⁺ A conductor.

The conductivity of the target lithium aluminum chloride derived compound is then predicted using de novo computational molecular dynamics (AIMD) simulation. The initial structure was allowed to statically relax and set to an initial temperature of 100K. The structure is then heated to a target temperature at a constant rate over a period of 2ps by a speed scale(550-650K). The total time of AIMD simulation is in the range of 400 to 1000 ps. A typical example of the calculated diffusivity as a function of temperature is shown in figure 11. Li at different temperatures of 500-650K ⁺ The diffusivity follows an arrhenius-type relationship.

Applying equation (I), the diffusivity at 300K is determined, and then the relationship between the conductivity and diffusivity of equation (II) can be used to determine the conductivity.

Accordingly, the first embodiment provides a solid state lithium ion electrolyte comprising: at least one material selected from the group of materials consisting of compounds of formulae (I), (II), (III) and (IV):

Li _x-y (M1) _y ZnCl ₄ (I)

wherein the method comprises the steps of

y is a number greater than 0 and less than 1, x is a value such that charge neutrality of the formula is obtained, and M1 is at least one element other than Li selected from elements of groups 1, 2, and 13;

Li _x Zn _1-z (M2) _z Cl ₄ (II)

wherein the method comprises the steps of

Li _x ZnCl _4-h (X) _h (III)

wherein the method comprises the steps of

Li _x-m (M1) _m Zn _1-n (M2) _n Cl _4-o (X) _o (IV)

wherein the method comprises the steps of

m is a number from 0 to less than 1, n is a number from 0 to less than 1, o is a number from 0 to less than 4, and x is a value such that formula (IV) is charge neutral, provided that at least two of m, n and o cannot be 0,

The compounds of the formulae (I) - (IV) are compounds having the space group Pmn2 ₁ Li of rhombohedral phase lattice structure ₂ ZnCl ₄ Is a derivative of the above. Pmn2 is depicted in FIG. 1 ₁ Li of space group ₂ ZnCl ₄ And the wavelength-based for this spatial group is shown in figure 2

X-ray diffraction (XRD) pattern of Cu-ka radiation. The peak positions and relative intensities are shown in fig. 3.

The inventors have determined that at Pmn2 ₁ Li of space group ₂ ZnCl ₄ Substitution of element M1 for Li, M2 for Zn, and X for Cl can enhance Li ion mobility and increase Li ion density within the lattice to provide an effective Li ion conductor that can be used as a solid electrolyte for lithium batteries.

Can be in Li ₂ ZnCl ₄ Is performed in (1) and still retains Pmn2 ₁ The degree of doping or substitution of the morphology varies with the element used as the dopant. In general, the more similar the ionic radius and electronic structure, the greater the molar amount of dopant that can be used without significant change in crystal morphology. The simulation method applied and described herein can be used to determine that the basic Pmn2 can be unchanged ₁ The degree of doping with a given element in the case of a crystalline structure.

For example, as described in the examples, al ³⁺ Can be doped with Zn ²⁺ To a ratio of 0.75Al/0.25Zn and retain Pmn2 ₁ Structure is as follows.

In other aspects of the first embodiment, the following simulation studies have been determined: the solid electrolytes of formulae (I) to (IV) can have a lithium ion (Li) at 300K of 0.01 to 10mS/cm, preferably 0.1 to 15mS/cm ⁺ ) Conductivity.

In addition, the activation energy of the solid state electrolytes of formulas (I) to (IV) may be 0.15 to 0.40eV.

The synthesis of the composite materials of the above embodiments may be accomplished by solid state reaction between stoichiometric amounts of the selected precursor materials. Exemplary methods of solid state synthesis are described, for example, in each of the following documents: i) Monatsheftef cur Chemie,100,295-303,1969; ii) Journal of Solid State Chemistry,128,1997,241; iii) Zeitschrift f u r Naturforschung B,50,1995,1061; iv) Journal of Solid State Chemistry 130,1997,90; v) Journal of Alloys and Compounds,645,2015, s174; and vi) Z.Naturasch.51b, 199652 5.

In a further embodiment, the present application includes a solid state lithium ion battery comprising the above solid state electrolyte. Solid state batteries of these embodiments, including metal-to-metal solid state batteries, may have higher charge/discharge rate performance and higher power density than conventional batteries, and may have the potential to provide high power and energy density.

Thus, in a further embodiment, a solid state lithium battery is provided. The solid-state lithium battery includes: an anode; a cathode; and a solid state lithium ion electrolyte located between the anode and the cathode; wherein the solid state lithium ion electrolyte comprises at least one material selected from the group of materials consisting of compounds of formulas (I), (II), (III), and (IV):

Li _x-y (M1) _y ZnCl ₄ (I)

wherein the method comprises the steps of

Li _x Zn _1-z (M2) _z Cl ₄ (II)

wherein the method comprises the steps of

Li _x ZnCl _4-h (X) _h (III)

wherein the method comprises the steps of

Li _x-m (M1) _m Zn _1-n (M2) _n Cl _4-o (X) _o (IV)

wherein the method comprises the steps of

The anode may be any anode structure conventionally employed in lithium ion batteries. In general, such materials are capable of inserting and extracting Li ⁺ Ions. Example anode active materials may include graphite, hard carbon, lithium Titanate (LTO), tin/cobalt alloys, and silicon/carbon composites. In one aspect, the anode may include a coating of lithium ion active material on the current collector. Standard current collector materials include, but are not limited to, aluminum, copper, nickel, stainless steel, carbon paper, and carbon cloth. In aspects advantageously configured with the solid state lithium ion conducting materials described in the first and second embodiments, the anode may be lithium metal or a lithium metal alloy, optionally coated on a current collector. In one aspect, the anode may be a sheet of lithium metal that serves as both the active material and the current collector.

The cathode structure may be any structure conventionally employed in lithium ion batteries including, but not limited to, composite lithium metal oxides such as lithium cobalt oxide (LiCoO) ₂ ) Lithium manganese oxide (LiMn) ₂ O ₄ ) Lithium iron phosphate (LiFePO) ₄ ) Andlithium nickel manganese cobalt oxide. Other active cathode materials may also include elemental sulfur and metal sulfide complexes. The cathode may also include current collectors such as copper, aluminum, and stainless steel.

In one aspect, the active cathode material may be a transition metal, preferably silver or copper. The transition metal-based cathode may not include a current collector.

In another set of embodiments, electrodes comprising solid electrolyte materials of formulas (I) - (IV) are also disclosed. Thus, in the preparation of the electrode, the active material as described above may be physically mixed with the solid electrolyte material prior to application to the current collector, or the solid electrolyte material may be applied as a coating on the applied active material. In either embodiment, the presence of a lithium ion superconductor on or within the electrode structure can enhance the performance of the electrode and can be used to protect conventional solid state electrolytes, particularly when applied as a coating.

Accordingly, embodiments of the present disclosure include a cathode comprising a current collector and a cathode active material layer applied to the current collector, wherein at least one of the following components is present: i) The cathode active material applied to the current collector is a physical mixture containing at least one of the solid electrolyte materials of formulas (I) - (IV) as described above; and ii) the cathode active material layer applied to the current collector is coated with a layer containing at least one of the solid electrolyte materials of formulas (I) - (IV). In the present disclosure, a cathode having both elements i) and ii) is also included.

In a related embodiment, the present disclosure includes an anode comprising a current collector and an anode active material layer applied to the current collector, wherein at least one of the following components is present: i) The anode active material applied to the current collector is a physical mixture containing at least one of the solid electrolyte materials of formulas (I) - (IV) as described above; and ii) the anode active material layer applied to the current collector is coated with a layer containing at least one of the solid electrolyte materials of formulas (I) - (IV).

A battery containing the cathode described in the above embodiment, the anode described in the above embodiment, or both the anode and the cathode according to the above embodiment is also an embodiment of the present disclosure.

Examples

Research of Li using de novo computational dynamics simulation _1.5 Zn _0.5 Al _0.5 Cl ₄ And Li (lithium) _1.25 Al _0.75 Zn _0.25 Cl ₄ To determine the conductive properties of these compounds and their derivatives. The initial structure was allowed to statically relax and set to an initial temperature of 100K. The structure was then heated to the target temperature (500-650K) at a constant rate over a period of 2ps by a speed scale. The total time of AIMD simulation is in the range of 400 to 1000 ps. Li at different temperatures of 500-650K ⁺ The diffusivity follows an arrhenius-type relationship.

Both compounds have rhombic space group Pmn2 ₁ Li of lattice structure ₂ ZnCl ₄ Is a doped derivative of (a). Li (Li) ₂ ZnCl ₄ The crystal structure of (2) is shown in figure 1. FIG. 2 shows Li ₂ ZnCl ₄ XRD analysis of the crystal structure of (c) and fig. 3 shows that the list is as in Li in fig. 2 ₂ ZnCl ₄ A table of peak positions and intensities of peaks having a maximum intensity compared to peaks having a relative intensity of 1 or more in XRD analysis. FIG. 10 shows Li ₂ ZnCl ₄ Arrhenius plot of Li ion diffusivity D versus temperature.

Li from AIMD simulation ₂ ZnCl ₄ Substituted compound and LiAlCl ₄ Li ion conductivity at 500K and E _hull (Energy above the hull) is shown in the following table.

Composition of the composition	E _hull (meV/atom)	σ(mS/cm)(500K)
			Li ₂ ZnCl ₄	12	39
Li _1.5 Al _0.5 Zn _0.5 Cl ₄	13	280
			Li _1.25 Al _0.75 Zn _0.25 Cl ₄	6	198
LiAlCl ₄	0	＜30

Li _1.25 Al _0.75 Zn _0.25 Cl ₄ Is 0.25.+ -. 0.06eV, li _1.25 Al _0.75 Zn _0.25 Cl ₄ Li ion conductivity at 300K was 14.1mS cm ^-1 It has an error limit of [1.0mS cm ] ^-1 ，193.3mS cm ^-1 ]，E _hull 6meV per atom, and Li _1.25 Al _0.75 Zn _0.25 Cl ₄ Is relative to Li/Li ⁺ 1.91 to 4.21V. E (E) _hull Is the energy difference between a compound and its stable phase equilibrium, which is generally used as a descriptor to demonstrate the metastability and synthesizability of the compound. Li (Li) ₂ ZnCl ₄ E of (2) _hull (12 meV/atom) is lower than 30 meV/atom, which implies the synthesizability of the experiment (see A.H.Nolan, Y.Zhu, X.He, Q.Bai, Y.Mo, joule 2018,22016).

FIG. 4 shows Pmn2 ₁ Li in space group _1.5 Zn _0.5 Al _0.5 Cl ₄ Is a crystal structure of (a). FIG. 5 shows Li _1.5 Zn _0.5 Al _0.5 Cl ₄ XRD analysis of the crystal structure of (c) and fig. 6 shows that Li listed in fig. 5 _1.5 Zn _0.5 Al _0.5 Cl ₄ A table of peak positions and intensities of peaks having a maximum intensity compared to peaks having a relative intensity of 1 or more in XRD analysis.

FIG. 7 shows Li _1.25 Al _0.75 Zn _0.25 Cl ₄ Is a crystal structure of (a). FIG. 8 shows Pmn2 ₁ Li in space group _1.75 Zn _0.75 Al _0.25 Cl ₄ XRD analysis of the crystal structure of (c) and fig. 9 shows that Li listed in fig. 8 _1.25 Al _0.75 Zn _0.25 Cl ₄ A table of peak positions and intensities of peaks having a maximum intensity compared to peaks having a relative intensity of 1 or more in XRD analysis.

FIGS. 11, 12 and 13 show Li obtained from AIMD simulation respectively ₂ ZnCl ₄ 、Li _1.5 Zn _0.5 Al _0.5 Cl ₄ And Li (lithium) _1.25 Al _0.75 Zn _0.25 Cl ₄ The Li ion probability density in (c). The probability density of lithium ions extracted from AIMD simulations counts the fraction of Li ions in each spatial position in the crystal structure (see he.x, zhu, y.and Mo, y.nat com 8, 15893 (2017)). The lithium ion probability densities in fig. 11, 12 and 13 show good channels for Li ion conduction in the crystal structure. For Al doping material and Li ₂ ZnCl ₄ The high probability of Li ion hopping of (a) demonstrates that favorable lithium ion conductivity is obtained with the compounds of formulas (I) - (IV).

Therefore, have Pmn2 ₁ These materials in the crystal form of the space group have excellent properties necessary for use as a high lithium ion conductive solid electrolyte, a protective coating for an electrode, or an active component for an electrode.

The previous description is provided to enable any person skilled in the art to make or use the present invention, and is provided in the context of a particular application and its requirements. Various modifications to the preferred embodiment will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the invention. Thus, the present invention is not limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein. In this regard, it is broadly contemplated that some embodiments within the invention may not illustrate every benefit of the invention.

Claims

1. A solid state lithium ion electrolyte comprising: at least one material selected from the group of materials consisting of compounds of formulae (I), (II), (III) and (IV):

Li _x-y (M1) _y ZnCl ₄ (I)

wherein the method comprises the steps of

Li _x Zn _1-z (M2) _z Cl ₄ (II)

wherein the method comprises the steps of

Li _x ZnCl _4-h (X) _h (III)

wherein the method comprises the steps of

Li _x-m (M1) _m Zn _1-n (M2) _n Cl _4-o (X) _o (IV)

wherein the method comprises the steps of

wherein the compounds of formulae (I), (II), (III) and (IV) comprise a compound having the steric group Pmn2 ₁ Is of the rhombic phaseLattice structure, and

2. The solid state lithium ion electrolyte of claim 1, wherein lithium ions (Li ⁺ ) The conductivity is 0.1 to 15mS/cm at 300K.

3. The solid state lithium ion electrolyte of claim 1, wherein the material has an activation energy of 0.15 to 0.40eV.

4. The solid state lithium ion electrolyte of claim 1, wherein the wavelength-based is

The calculated XRD analysis of Cu-K alpha radiation of (C) includes peaks defining Pmn2 ₁ Space group:

peak position Relative intensity 16.94396 100.0 17.38112 79.78 17.44439 38.38 18.97989 27.12 18.97994 27.12 21.52424 18.63 25.27256 72.75 26.35011 48.76 27.57174 74.31 28.80964 17.24 28.80967 17.25 28.88812 12.98 28.88814 12.98 29.80676 13.60 29.80682 13.60 43.85879 31.83 45.85439 52.96 49.47720 11.07 49.47726 11.07 49.62647 10.82 49.62652 10.82 51.89181 11.78 52.68764 12.57

。

5. A solid state lithium battery comprising:

an anode;

a cathode; and

a solid lithium ion electrolyte between the anode and the cathode,

Li _x-y (M1) _y ZnCl ₄ (I)

wherein the method comprises the steps of

Li _x Zn _1-z (M2) _z Cl ₄ (II)

wherein the method comprises the steps of

Li _x ZnCl _4-h (X) _h (III)

wherein the method comprises the steps of

Li _x-m (M1) _m Zn _1-n (M2) _n Cl _4-o (X) _o (IV)

wherein the method comprises the steps of

wherein the compounds of formulae (I), (II), (III) and (IV) comprise a compound having the steric group Pmn2 ₁ And is of rhombohedral phase lattice structure

6. The solid state lithium ion battery of claim 5, wherein the battery is a lithium metal battery or a lithium ion battery.

7. An electrode for a solid state lithium battery comprising:

a current collector; and

an electrode active layer on the current collector,

wherein the electrode active layer comprises at least one compound selected from the group consisting of compounds of formulas (I), (II), (III), and (IV):

Li _x-y (M1) _y ZnCl ₄ (I)

wherein the method comprises the steps of

Li _x Zn _1-z (M2) _z Cl ₄ (II)

wherein the method comprises the steps of

Li _x ZnCl _4-h (X) _h (III)

wherein the method comprises the steps of

Li _x-m (M1) _m Zn _1-n (M2) _n Cl _4-o (X) _o (IV)

wherein the method comprises the steps of

8. An electrode for a solid state lithium battery comprising:

a current collector;

an electrode active layer on the current collector; and

a coating layer on the electrode active layer,

Li _x-y (M1) _y ZnCl ₄ (I)

wherein the method comprises the steps of

Li _x Zn _1-z (M2) _z Cl ₄ (II)

wherein the method comprises the steps of

Li _x ZnCl _4-h (X) _h (III)

wherein the method comprises the steps of

Li _x-m (M1) _m Zn _1-n (M2) _n Cl _4-o (X) _o (IV)

wherein the method comprises the steps of

m is a number from 0 to less than 2, n is a number from 0 to less than 1, o is a number from 0 to less than 4, and x is a value such that the formula (IV) is charge neutral, provided that at least two of m, n and o cannot be 0,

9. A solid state lithium battery comprising the electrode of claim 7, wherein the solid state lithium battery is a lithium ion battery or a lithium metal battery.

10. A solid state lithium battery comprising the electrode of claim 8, wherein the solid state lithium battery is a lithium ion battery or a lithium metal battery.